Aerobic Aliphatic Hydroxylation Reactions by Copper Complexes: A Simple Clip-and-Cleave Concept.

A simple imine clip-and-cleave concept has been developed for the selective hydroxylation of non-activated CH bonds in aliphatic aldehydes with dioxygen through a copper complex. The synthetic protocol involves reaction of a substrate aldehyde with N,N-diethyl-ethylendiamine to give the corresponding imine, which is used as a bidentate donor ligand forming a copper(I) complex with [Cu(CH CN) ][CF SO ]. After exposure of the reaction mixture to dioxygen acidic cleavage and aqueous workup liberates the corresponding β-hydroxylated aldehyde.

Beyond the corey reaction II: dimethylenation of sterically congested ketones.

Bulky methyl ketones show significantly decreased reactivities toward the Corey-Chaykovsky methylenation reagent dimethylsulfoxonium methylide (DMSM). The excess of base and temperature increase opens an alternative reaction channel that instead leads to the corresponding cyclopropyl ketones. Computations suggest that the initial reaction step involves the methylene group transfer from DMSM on the ketone enolate followed by the intramolecular cyclization.

Unconventional molecule-resolved current rectification in diamondoid-fullerene hybrids.

The unimolecular rectifier is a fundamental building block of molecular electronics. Rectification in single molecules can arise from electron transfer between molecular orbitals displaying asymmetric spatial charge distributions, akin to p-n junction diodes in semiconductors. Here we report a novel all-hydrocarbon molecular rectifier consisting of a diamantane-C60 conjugate.

Stereospecific consecutive epoxide ring expansion with dimethylsulfoxonium methylide.

Consecutive ring-expansion reactions of oxiranes with dimethylsulfxonium methylide were studied experimentally and modeled computationally at the density functional theory (DFT) and second-order Møller-Plesset (MP2) levels of theory utilizing a polarizable continuum model (PCM) to account for solvent effects. While the epoxide to oxetane ring expansion requires 13-17 kcal mol(-1) activation and occurs at elevated temperatures, the barriers for the ring expansions to oxolanes are higher (ca. 25 kcal mol(-1)) and require heating to 125 °C.

Metal oxide-organic frameworks (MOOFs), a new series of coordination hybrids constructed from molybdenum(VI) oxide and bitopic 1,2,4-triazole linkers.

A series of molybdenum(VI) oxide-organic solids were prepared by hydrothermal reactions employing N-donor tectons, which combine two 1,2,4-triazol-4-yl sites separated by representative aliphatic spacers (ethylene, tr(2)eth; 1,3-propylene, tr(2)pr; trans-1,4-cyclohexanediyl, tr(2)cy; diamondoid 1,3-adamantanediyl, tr(2)ad; 1,6- and 4,9-diamantanediyls, 1,6-tr(2)dia and 4,9-tr(2)dia) and heterofunctional 5-[4-(1,2,4-triazol-4-yl)phenyl]tetrazole (trtz). In all the compounds the 1,2,4-triazol-4-yl group acts as a short-distance N(1),N(2)-bridge between two Mo ions (Mo-N 2.36-2.

Beyond the corey reaction: one-step diolefination of cyclic ketones.

The reactivities of the cyclic ketones cycloheptanone, cyclodecanone, and cycloundecanone with dimethylsulfoxonium methylide generated from trimethylsulfoxonium iodide and base (NaH) were studied in diglyme at 130 degrees C. Oxiranes, which primarily form via the Corey reaction, lead to ring expansions to give oxetanes and oxacyclopentanes when an excess of dimethylsulfoxonium methylide is used. The Corey reaction is suppressed in the presence of excess of base, and 1,3-terminal dienes form instead (we term this reaction the Yurchenko diolefination).

Simple preparation of diamondoid 1,3-dienes via oxetane ring opening.

The transformations of apical mono- and bisacetyl diamondoids to the respective oxetanes and subsequent acid-catalyzed ring opening/dehydration lead to diamondoidyl mono- and bis-1,3-dienes in high preparative yields.